CN111278419A

CN111278419A - Oil-in-water emulsion composition and cosmetic

Info

Publication number: CN111278419A
Application number: CN201880069343.XA
Authority: CN
Inventors: 高田有子; 生方早央里; 多和田华子; 竹胁一幸
Original assignee: Shin Etsu Chemical Co Ltd
Current assignee: Shin Etsu Chemical Co Ltd
Priority date: 2017-10-27
Filing date: 2018-10-24
Publication date: 2020-06-12
Anticipated expiration: 2038-10-24
Also published as: US20210177709A1; EP3701933A4; JPWO2019082911A1; WO2019082911A1; EP3701933A1; CN111278419B; JP7014229B2

Abstract

An oil-in-water emulsion composition comprising the components (A), (B) and (C). (A) A silicone resin composition which is a mixture obtained by mixing the component (A-1) and the component (A-2) in a specific mass ratio and has a viscosity of 100 to 4000mm at 25 DEG C²S: 30 to 70% by mass of (A-1) having [ R ] in a specific molar ratio₃SiO_0.5]Unit and [ SiO₂]A silicone resin of units, (a-2) a volatile oil; (B) the average addition mole number of Ethylene Oxide (EO) is 10 or morePolyoxyethylene sorbitan fatty acid ester having an HLB of 11 or more: 2-10 mass%; (C) water: 20 to 62 mass%.

Description

Oil-in-water emulsion composition and cosmetic

Technical Field

The present invention relates to an oil-in-water type emulsion composition and a cosmetic containing a silicone resin.

Background

In the field of makeup cosmetics such as eye makeup such as mascara and skin care, resins having water resistance, oil resistance and prevention of makeup removal have been developed in order to impart good properties to the cosmetics. As the resin, it is important that makeup is difficult to be removed and makeup sustainability is excellent, and silicone oil or silicone resin having water repellency is used in a large amount. Examples of the silicone oil and silicone resin having water repellency used in cosmetics include silicone resins or silicone crosslinked products obtained by addition polymerization of organohydrogenpolysiloxanes and vinyl-containing organopolysiloxanes, acrylic-silicone graft copolymers, and the like (patent document 1: japanese patent laid-open No. 2009-9814, patent document 2: japanese patent No. 2796856, patent document 3: japanese patent laid-open No. 2704730, and patent document 4: japanese patent laid-open No. 2017-66092). Among them, the hardness of a coating film can be easily adjusted by changing the ratio of crosslinking units and the degree of polymerization, and therefore, silicone resins have been used in a large number of cosmetics by differentiating the utilization structure according to the use of the cosmetics.

In recent years, from the viewpoint of environmental load and skin irritation, oil-in-water emulsion compositions containing silicone resins have been used in a large amount in cosmetic compositions, as well as water-in-oil cosmetic compositions (patent document 5: japanese patent No. 4846423). Since the silicone resin is a solid or a highly viscous liquid and is difficult to emulsify as it is, it is generally dissolved in a hydrocarbon solvent such as isododecane or a low-viscosity silicone oil and mixed with a surfactant to emulsify. In the case of cosmetics, a solvent is used in an amount equal to or greater than that of a silicone resin when the silicone resin is dissolved, and the solvent may inhibit the properties of the silicone resin and may cause irritation to the skin (patent document 1: japanese patent laid-open No. 2009-9814, patent document 4: japanese patent laid-open No. 2017-66092, patent document 5: japanese patent laid-open No. 4846423, patent document 6: japanese patent laid-open No. 3220953). Therefore, an oil-in-water type emulsion composition having a small proportion of a hydrocarbon solvent such as a silicone resin and isododecane, a low viscosity silicone oil, or the like is required. However, if the proportion of a hydrocarbon solvent such as isododecane or a low-viscosity silicone oil to a silicone resin is small, there is a possibility that cracks may occur in the coating film, solid may precipitate, or repulsion may occur in the coating film, and furthermore, it is difficult for the emulsified particles of the oil-in-water type emulsified composition to have a small particle size, and separation of the concentration and the lightness may occur over time. Heretofore, there has been proposed an emulsion composition of a silicone resin obtained by blending and emulsifying a specific water-miscible organic solvent in an amount of 5 to 25 mass% relative to the silicone resin (patent document 7: Japanese patent No. 5163888, patent document 8: Japanese patent laid-open No. 2008-138059), but these solvents are not solvents that can be used in cosmetics, and therefore, an emulsion composition of a silicone resin using a small amount of a solvent that can also be used in cosmetics is required.

In addition, as a surfactant for emulsifying a silicone resin, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene decyl ether are generally used (patent document 6: Japanese patent No. 3220953, patent document 7: Japanese patent No. 5163888, and patent document 8: Japanese patent laid-open No. 2008-138059), but these surfactants have irritation to the skin and are concerned about their use. Therefore, it is necessary to use a surfactant which is less irritating to the skin and less harmful to the body even when it is introduced into the body, but a polyglycerol fatty acid ester which is less irritating and has been approved as a food additive is weak in emulsifying power, and an oil-in-water type emulsion composition emulsified with the polyglycerol fatty acid ester or the like may be separated into different colors over a long period of time.

As can be seen from the above, there is a need for an oil-in-water emulsion composition of silicone resins comprising: when the cosmetic composition is blended with a makeup cosmetic composition such as an eye makeup composition such as mascara, a skin care composition or the like, the persistence of the cosmetic composition (makeup durability) is further improved, cracks, precipitation of solids, and repulsion in the cosmetic composition are small, the irritation to the skin is small, the damage is small even if the cosmetic composition enters the body, and the storage stability is good.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2009-9814

Patent document 2: japanese patent No. 2796856

Patent document 3: japanese patent No. 2704730

Patent document 4: japanese patent laid-open publication No. 2017-66092

Patent document 5: japanese patent No. 4846423

Patent document 6: japanese patent No. 3220953

Patent document 7: japanese patent No. 5163888

Patent document 8: japanese laid-open patent publication No. 2008-138059

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an oil-in-water emulsion composition containing a silicone resin, which, when added to a makeup cosmetic such as an eye makeup such as mascara or a skin care cosmetic, further improves the persistence of the cosmetic, is less likely to cause repulsion, cracks, and deposition of solids on the skin, has little irritation to the skin, causes little damage even when it enters the body, and has good storage stability, and a cosmetic containing the same.

Means for solving the problems

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that: mixing (A) a specific silicone resin (A-1) and a volatile oil (A-2) at a specific ratio, wherein the viscosity at 25 ℃ is 100 to 4000mm²The silicone resin composition can solve the above problems by using an oil-in-water emulsion cosmetic in which (B) a polyoxyethylene sorbitan fatty acid ester having an average number of moles of Ethylene Oxide (EO) added of 10 or more and an HLB of 11 or more is emulsified, and the present invention has been accomplishedThe invention relates to a method for preparing a novel high-performance composite material. More specifically, the ratio of the (A-1) silicone resin to the (A-2) volatile oil is 70/30-92/8, and the proportion of the (A-2) volatile oil is less than that of a conventional product in which the silicone resin is dissolved, so that the properties of the (A-1) silicone resin are not easily impaired, and the irritation of the volatile oil or the like to the skin is small. Further, the viscosity of the silicone resin composition (A) is selected to be 100 to 4000mm²The silicone resin in the range of/s can be emulsified by a general MIXER such as HOMO MIXER and HOMO DISPER without using a special device such as a high pressure homogenizer, and the oil-in-water type emulsion composition produced by this method has fine emulsion particles and is stable without causing separation of shade over time. Further, the oil-in-water emulsion composition of the present invention uses a polyoxyethylene sorbitan fatty acid ester which is also recognized as a food additive, and therefore, is less irritating to the skin and less harmful even when it enters the body.

Accordingly, the present invention provides the following oil-in-water emulsion composition and cosmetic.

1. An oil-in-water emulsion composition comprising the following components (A), (B) and (C),

(A) a silicone resin composition which is a mixture obtained by mixing a component (A-1) and a component (A-2) in a mass ratio represented by (A-1)/(A-2) of 70/30-92/8 and has a viscosity at 25 ℃ of 100-4000 mm²S: 30 to 70% by mass of a binder,

(A-1) has [ R ]₃SiO_0.5]Unit and [ SiO₂]Unit, with [ R₃SiO_0.5]Unit/[ SiO ]₂]A silicone resin having a molar ratio of units of 0.7 to 1.4, (wherein R is a 1-valent organic group having 1 to 10 carbon atoms, which may be the same or different)

(A-2) a volatile oil,

(B) polyoxyethylene sorbitan fatty acid esters having an average number of moles of Ethylene Oxide (EO) added of 10 or more and an HLB of 11 or more: 2 to 10% by mass of a binder,

(C) water: 20 to 62 mass%.

The oil-in-water emulsion composition according to claim 1, wherein the emulsified particles have an average particle diameter of 400nm or less.

3.1 or 2, wherein the component (A-2) is selected from hydrocarbon oils and oil-in-water emulsion compositions having a viscosity of 2mm at 25 ℃²1 or more volatile oils in silicone oil with a concentration of less than or equal to s.

The oil-in-water emulsion composition according to any one of claims 1 to 3, wherein the component (B) is at least 1 selected from the group consisting of polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate and polyoxyethylene sorbitan monopalmitate.

The oil-in-water emulsion composition according to any one of claims 1 to 4, wherein the component (A-1) is represented by the formula [ R ]₃SiO_0.5]Unit/[ SiO ]₂]The molar ratio of the units is 1.1 to 1.4.

6.1 to 5, wherein the component (A-1) is a liquid silicone resin of 5000 mPas or more at 36 ℃.

7.1 to 6, further comprising 0.1 to 5% by mass of (D) a component selected from the group consisting of 1, 3-butanediol, glycerin, maltitol, sorbitol, 1, 2-pentanediol, 1, 2-hexanediol, polyethylene glycol and trimethylglycine.

8.1 to 7, further comprising 0.1 to 5% by mass of (E) a water-soluble polymer compound.

9.1 to 8, further comprising (F) synthetic amorphous silica in an amount of 0.1 to 10 mass%.

10. A cosmetic preparation comprising the oil-in-water emulsion composition according to any one of 1 to 9.

ADVANTAGEOUS EFFECTS OF INVENTION

An oil-in-water emulsion composition containing a silicone resin, which, when added to a make-up cosmetic such as an eye makeup such as mascara or a skin care cosmetic, further improves the persistence of the cosmetic, is less likely to cause repulsion, cracking, and precipitation of solids on the skin, has low irritation to the skin, is less harmful even when it enters the body, and has good storage stability, and a cosmetic containing the same can be provided.

Detailed Description

The present invention will be described in detail below.

[ (A) component ]

(A) The component (A) is a mixture obtained by mixing the following component (A-1) and component (A-2) in a mass ratio of (A-1)/(A-2) of 70/30-92/8, and the viscosity at 25 ℃ is 100-4000 mm²A silicone resin composition.

(A-1) has [ R ]₃SiO_0.5]Unit and [ SiO₂]Unit of [ R ]₃SiO_0.5]Unit/[ SiO ]₂]A silicone resin having a molar ratio of units of 0.7 to 1.4

(wherein R is the same or different 1-valent organic group having 1 to 10 carbon atoms.)

(A-2) volatile oil

The component (A-1) is a compound having [ R ]₃SiO_0.5]Unit and [ SiO₂]Unit of [ R ]₃SiO_0.5]Unit/[ SiO ]₂]The unit represents a molar ratio of 0.7 to 1.4, and 1 kind of the silicone resin may be used alone or 2 or more kinds may be used in combination as appropriate. In the formula, R is the same or different 1-valent organic groups having 1 to 10 carbon atoms, and specific examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, and cycloheptyl, aryl groups such as phenyl, and alkenyl groups such as vinyl and allyl. Among them, methyl group or phenyl group is preferable, and methyl group is particularly preferable from the viewpoint of general versatility.

From [ R ]₃SiO_0.5]Unit/[ SiO ]₂]The molar ratio of the units is 0.7 to 1.4, preferably 1.1 to 1.4. If the content is less than 0.7, the coating film becomes hard, and cracks or solid precipitates may occur in the coating film. If it exceeds 1.4, the film is too soft, and when used as a cosmetic film, the effect of sustainability is not exhibited. Furthermore, except for [ R ]₃SiO_0.5]Unit and [ SiO₂]In addition to the unit, may further have [ R ]₂SiO]Unit or [ RSiO_1.5]And (4) units. [ R ]₃SiO_0.5]Unit and [ SiO₂]The total unit content of the units is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, and still more preferably 80 to 100 mol% of all siloxane units. In addition, [ R ]₂SiO]The content of the unit may be 0 to 70 mol%, preferably 0 to 50 mol%, based on the total siloxane units. If the amount exceeds 50%, the coating film is too soft, and when the oil-in-water emulsion composition is blended in a cosmetic, the effect of sustainability may not be exhibited. [ RSiO ]_1.5]The content of the unit may be 0 to 50 mol%, preferably 0 to 20 mol%, based on the total siloxane units. If the amount exceeds 50%, stickiness may occur when the oil-in-water emulsion composition is blended into a cosmetic.

The component (A-1) may contain SiOH group or SiOR group¹And (4) a base. Then R¹Examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl and cycloheptyl, and aryl groups such as phenyl. In this case, [ HOSiO ]_1.5]Unit, [ R ]¹OSiO_1.5]Units, etc. contain. The content of SiOH groups is not particularly limited, and when contained, it is preferably 0.015 to 0.3mol/100 g. When the ratio is larger than 0.3mol/100g, in the oil-in-water type emulsion composition, either the SiOH groups or the SiOH groups and SiOR groups of the silicone resin are in between¹The polymerization degree of the silicone resin may vary by radical reaction. In addition, as SiOR¹The content of the base is not particularly limited, but is preferably 0 to 0.5mol/100 g. SiOR of silicone resin (A-1) in oil-in-water emulsion composition¹The radicals slowly hydrolyze to give the alcohol if SiOR¹When the content of the base is 0.5mol/100g or more, the amount of alcohol produced by hydrolysis increases, and the alcohol may interfere with the properties of the cosmetic.

Further, the weight average molecular weight of the component (A-1) is preferably 800 to 20000, more preferably 1000 to 6000, and further preferably 1000 to 3000. If the weight average molecular weight is less than 800, the oil-in-water emulsion composition may not exhibit sustained effects when blended in a cosmetic. On the other hand, if it exceeds 20000, the coating becomes hard, and cracks, solid precipitation, or repelling may occur in the coating. The weight average molecular weight in the present invention is a weight average molecular weight in terms of polystyrene obtained by GPC analysis. Further, the component (A-1) is preferably a liquid silicone resin having a viscosity of 5000 mPas or more at 36 ℃ which is a body temperature of a human being. Specifically, a silicone resin is put into a container at 36 ℃, and if the container is tilted by 90 degrees, the shape of the silicone resin is deformed within 1 hour. By using a liquid silicone resin having fluidity at 36 ℃, a coating film free from deposition of solids can be formed without causing coating unevenness or cracks even when applied to human skin. Further, the absolute viscosity of the component (A-1) is preferably 5000 mPas or more, more preferably 8000 mPas or more at 36 ℃. If the absolute viscosity of the silicone resin (A-1) is less than 5000 mPas at 36 ℃, the effect of sustainability may not be exhibited when the oil-in-water emulsion composition is blended with a cosmetic. The absolute viscosity of the component (A-1) is measured by a BM type rotational viscometer.

The component (A-1) can be produced by a known method. For example, the silane compound can be obtained by subjecting chlorosilane or alkoxysilane to hydrolysis and condensation reaction. For example, for silicone resins that are MQ resins, after adding methanesulfonic acid to a solution of hexamethylsiloxane and ethyl silicate or ethyl polysilicate in isopropanol, hydrolysis and condensation reactions are performed by dripping water and refluxing at about 80 ℃ for 8 hours. An alkaline aqueous solution is added to the obtained resin solution, and after neutralizing the acid, a hydrocarbon solvent or a low-viscosity silicone oil is added, and the alcohol component is distilled off by heating under reduced pressure, whereby a solution of the hydrocarbon solvent or the low-viscosity silicone oil of the MQ resin can be obtained.

[ (A-2) component ]

The volatile oil can be suitably selected from volatile oils that can be used in cosmetics and exhibit a boiling point of 260 ℃ or less at normal pressure and 25 ℃, and 1 type of volatile oil can be used alone or 2 or more types of volatile oils can be used in combination. Specific examples thereof include silicone oils, hydrocarbon oils, ester oils, and the like. Among them, silicone oils and hydrocarbon oils are preferable from the viewpoint of versatility.

As the silicone oil, a silicone oil having a viscosity of 2mm at 25 ℃ was used²Silicone oil with a concentration of less than s. The viscosity is a kinematic viscosity and is a measured value at 25 ℃ using an austenitic viscometer (the same applies hereinafter). If the viscosity exceeds 2mm²When the oil-in-water emulsion composition is blended into a cosmetic or the like, the silicone oil is less likely to volatilize at 25 ℃ and remains in the coating film, resulting in a sticky feeling. Examples of the silicone oil include those represented by the following general formula.

[ solution 1]

(wherein a is an integer of 1 to 3, R²The organic groups are same or different 1-valent organic groups with 1-10 carbon atoms, and n is an integer of 4-6. )

R is defined as²Examples of the same groups as those of R are given.

The hydrocarbon oil includes a linear or branched volatile hydrocarbon oil, and specific examples thereof include isododecane, α -olefin oligomer, light isoparaffin, light liquid isoparaffin, liquid paraffin, and liquid isoparaffin.

Examples of the ester oil include ethyl acetate, butyl acetate, and isopropyl acetate.

The mass ratio of the (A-1) organic silicon resin to the (A-2) volatile oil is (A-1)/(A-2) 70/30-92/8, preferably 80/20-90/10. If the proportion of the volatile oil (A-2) is greater than 70/30, cracks may occur when the cosmetic composition comprising the oil-in-water emulsion composition is applied, and the volatile oil (A-2) does not immediately volatilize, possibly hindering the properties of the cosmetic composition or causing irritation to the skin. On the other hand, if the silicone resin (A-1) is increased more than 92/8, the storage stability may be lowered and separation of shade may occur over time.

(A) The viscosity of the organic silicon resin composition is 100-4000 mm at 25 DEG C²(ii) s, preferably 200 to 2000mm²And s. If the viscosity of the silicone resin composition (A) is less than 100mm²In terms of/s, emulsification is difficult with a general MIXER such as HOMO MIXER or HOMO DISPER, and the emulsified particles of the oil-in-water type emulsified cosmetic are not thinned, and the storage stability is lowered, and separation of shade may occur over time. Further, if the viscosity ratio of the silicone resin composition (A) is 4000mm²When the amount/s is large, the storage stability of the oil-in-water emulsion cosmetic of the present invention is lowered, and separation of the color from the water may occur over time.

[ (B) component ]

(B) The component (B) is a polyoxyethylene sorbitan fatty acid ester having an average number of moles of Ethylene Oxide (EO) added of 10 or more and an HLB of 11 or more, and 1 kind of the polyoxyethylene sorbitan fatty acid ester may be used alone or 2 or more kinds may be used in combination as appropriate. By using such a sorbitan fatty acid ester, an oil-in-water emulsion composition having little irritation to the skin and excellent coating properties and storage stability can be realized.

Examples of the polyoxyethylene sorbitan fatty acid ester include monolauric acid polyoxyethylene sorbitan, monostearate polyoxyethylene sorbitan, monooleate polyoxyethylene sorbitan, monopalmitate polyoxyethylene sorbitan, isostearic acid polyoxyethylene sorbitan, trioleate polyoxyethylene sorbitan, tristearate polyoxyethylene sorbitan, and the like. Among them, from the viewpoint of emulsifiability, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan monopalmitate are preferable. Further, polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate are more preferable since they are also recognized as food additives.

The number of addition mols of ethylene oxide is 10 or more, preferably 10 to 100, more preferably 15 to 80. When the addition mole ratio of ethylene oxide is less than 10, the surfactant tends to remain in the coating film of the silicone resin (A-1), and thus the water resistance may be lowered and stickiness may occur.

The HLB is 11 or more, preferably 13 to 18, and more preferably 14 to 17. HLB is according to griffin's formula. When a liquid surfactant having an HLB of less than 11 is blended, the surfactant tends to remain in the coating film of the silicone resin (a-1), and thus the water repellency may be reduced and stickiness may occur.

It is known that surfactants having a small molecular weight, having functional groups such as amino groups, or containing a large amount of salts generally cause skin irritation. Therefore, in order to further reduce the irritation of the oil-in-water type emulsion composition of the present invention, a polyoxyethylene sorbitan fatty acid ester having a smaller content of salt and low-molecular compound may be selected.

[ (C) ingredient ]

Purified water or the like can be appropriately selected and used.

[ (D) component ]

In the oil-in-water type emulsion composition of the present invention, it is preferable to blend 1 or more selected from 1, 3-butanediol, glycerin, maltitol, sorbitol, 1, 2-pentanediol, 1, 2-hexanediol, polyethylene glycol, and trimethylglycine (D). (D) The components can be optionally blended in the oil-in-water emulsion composition, and 1 kind of the component can be used alone or 2 or more kinds can be used in combination as appropriate. Among them, 1, 3-butanediol, glycerin, and polyethylene glycol are preferable from the viewpoint of general versatility.

When the component (A) is emulsified, if the component (D) is blended, the emulsified particles of the oil-in-water type emulsion composition become fine, and the storage stability is further improved. Since the component (D) is a moisturizing agent, the oil-in-water emulsion composition can have an improved moisturizing ability when blended with the component (D), and can impart moisturization when applied to the skin after blended with a cosmetic.

[ (E) ingredient ]

In the oil-in-water type emulsion composition of the present invention, (E) a water-soluble polymer compound is preferably blended in order to suppress stickiness of the coating film, improve the strength of the coating film, further improve the persistence when blended in a cosmetic material, improve the emulsifiability, or thicken the oil-in-water type emulsion composition to improve the storage stability. The water-soluble polymer compound is a polymer compound having a polar group in the molecule and being dispersible in water. The water-soluble polymer compound may be a natural polymer compound, a semi-synthetic product, or a synthetic product. Specific examples thereof include starch, mannan, galactan as seaweed, alginate, gum arabic, dextran, gelatin, casein, collagen, polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, polyvinyl pyrrolidone, xanthan gum, and acrylic acid polymer. These can be used alone in 1 or more than 2 kinds of appropriate combination.

[ (F) ingredient ]

In the oil-in-water type emulsion composition of the present invention, it is preferable to blend the synthetic amorphous silica (F) in order to improve the stickiness of the coating film and to improve the sustainability of the cosmetic. The amorphous silica to be synthesized may be dry silica obtained by a combustion method in which silicon tetrachloride is burned in oxygen or hydrogen, or wet silica obtained by a precipitation method in which sodium silicate is neutralized with sulfuric acid, a gel method, or a sol-gel method in which alkoxysilane is hydrolyzed. The synthetic amorphous silica can be used alone in 1 kind or in appropriate combination of 2 or more kinds. The primary particle size of the synthesized amorphous silica is preferably 1 to 50nm, and the BET specific surface area is preferably 50 to 1000m²(ii) in terms of/g. The method of measuring the primary particles of the synthesized amorphous silica is a value converted from a specific surface area measurement value (according to JISZ8830) obtained by the BET adsorption method. When the synthetic amorphous silica is blended in a powder form in the oil-in-water type emulsion composition of the present invention, when the silicone resin composition (a) is blended at the time of emulsification or emulsified after being blended in advance in the silicone resin composition (a), the synthetic amorphous silica can be uniformly dispersed, and the separation of shade in the oil-in-water type emulsion composition becomes difficult. When the synthetic amorphous silica is mixed with the colloidal silica in a state of being dispersed in water, the colloidal silica may be mixed at the time of emulsifying the silicone resin composition (a) or may be mixed after the emulsification. As the synthetic amorphous silica, colloidal silica is preferable from the viewpoint of ease of compounding.

Specific examples of the component (F) include the following products. Examples of the powdery dry silica include RHEOSIL manufactured by Deshan corporation, HDK V15 manufactured by Asahi Kasei Wacker corporation, HDK N20, HDK T30, HDKT40, HDK H15, HDK H18, HDK H20, HDK H30, AEROSIL 50 manufactured by AEROSIL corporation, AEROSIL90G, AEROSIL 130, AEROSIL 200, AEROSIL 200CF, AEROSIL 200V, AEROSIL 200FAD, AEROSIL300, AEROSIL300 CF, AEROSIL 380, AEROSIL OX50, and AEROSIL TT 600. Examples of the powdery wet-process silica include NIPSIL, NIPGEL AZ-200, NIPGEL AZ-201, NIPGEL AZ-410, NIPGEL AZ-260, NIPGEL AZ-360, NIPGEL AZ-460, NIPGEL AZ-6A0, NIPGEL AY-200, NIPGEL AY-220, NIPGEL AY-420, NIPHEL AY-601, NIPGEL AY-6A3, NIPGEL AY-8A2, NIPGBY-001, NIPGEL BY-200, NIPGEL AY-400, NIPGEL BY-601, NIPGEL CX-200, NIPGEL CX-600, NIPGEL CY-200, NIPSIL 3, NIPSIL VN, NIPSIL BYLL LP, NIPSIL BYNA, NIPSIL 150, NIPSNS-150, NIPSIL-150, NIPSNS-150, NIPSEL-NS-150, NIPSIL-S-150, NIPSIL-200, NIPSIL NA, NIPSIL KP, NIPSIL L-300, NIPSIL KQ, NIPSIL NS-P, NIPSIL E-200A, NIPSIL E-220A, NIPSIL K ═ 500, NIPSIL E-1009, NIPSIL E-1011, NIPSIL E-1030, NIPSIL E-150J, NIPSIL E-170, NIPSIL E-200, NIPSIL E-220, NIPSIL E-743, NIPSIL E-75, NIPSIL HD-2, NIPSIL G-300, NIPSIL E-74P, NIPSIL N-300A, and the like. Examples of colloidal silica as an aqueous dispersion of synthetic amorphous silica include BINZIL 15/500, BINZIL 30/360, BINZIL 30/220, BINZIL30/80, BINZIL 305, BINZIL 40/220, BINZIL 40/130, BINZIL 50/80, NYAOL 215, NYAOL 830, NYAOL 1430, NYAOL 1440, NYAOL 2040, NYAOL 2050, NYAOL 9950, etc., SNOTEX 20, SNOTEX 30, SNOTEX 40, SNOTEX C, SNOTEX N, SNOTEX O, SNOTEX S, SNOTEX 20L, SNOTEX OL, etc., manufactured by Akzo Novel, and COSMO S-40, manufactured by Nissan Kagaku corporation, etc.

The amount of each component to be blended in the oil-in-water emulsion composition will be described below.

(A) The amount of the component (A) is 30 to 70% by mass, preferably 40 to 60% by mass. If the amount of the compound is less than 30% by mass, it becomes difficult to obtain the properties such as durability and water repellency when the compound is added to a cosmetic. On the other hand, if the content is more than 70% by mass, the viscosity of the oil-in-water emulsion composition of the present invention increases, and handling becomes difficult.

(B) The amount of the component (A) is 2 to 10% by mass, preferably 3 to 7% by mass. When the amount of the polyoxyethylene sorbitan fatty acid ester (B) is less than 2% by mass, the emulsified particles in the oil-in-water emulsion composition are not thinned, the storage stability is lowered, and there is a possibility that the separation of the concentration may occur. In addition, when an oil-in-water emulsion composition is applied, there is a possibility that repulsion occurs. On the other hand, if it is more than 10% by mass, the polyoxyethylene sorbitan fatty acid ester (B) may interfere with the properties of the silicone resin (a-1), and the durability and water resistance of the cosmetic may be reduced.

(C) The amount of the component (B) is 20 to 62% by mass, more preferably 30 to 55% by mass. If the amount is less than 20% by mass, the viscosity of the oil-in-water emulsion composition of the present invention increases, and handling becomes difficult. On the other hand, if the amount is more than 62% by mass, water (C) tends to remain, and the durability and water repellency of the cosmetic may be reduced.

(D) The component (B) is an optional component, and when it is blended, it is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass. The effect of blending component (D) is obtained by setting the blending amount of component (D) to 0.1 mass% or more. On the other hand, if the amount is more than 5% by mass, the properties of the silicone resin (A-1) may be impaired, and the durability and water resistance of the cosmetic may be lowered.

(E) The component (B) is an optional component, and when it is blended, it is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass. If the amount of the component (E) is 0.1% by mass or more, the effect of blending the component (E) is obtained, and if it is more than 5% by mass, the water repellency of the cosmetic material may be impaired.

(F) The component (B) is an optional component, and when it is blended, it is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass. When the amount of component (F) is 0.1 mass% or more, the effect of blending component (F) is obtained, and if it is more than 10 mass%, cracks may be generated in the coating film. In addition, various ingredients used in usual cosmetics can be blended in the oil-in-water emulsion composition of the present invention within a range not impairing the effects of the present invention.

[ production method ]

The present invention is a method for emulsifying a composition comprising the silicone resin composition (a), the polyoxyethylene sorbitan fatty acid ester (B), and water (C) by stirring (step (I)). More preferred examples are described in detail below.

(I) Emulsification step

The components (a), (B) and (C) are mixed and stirred at high speed using HOMO MIXER or HOMO DISPER to emulsify. When the components (A), (B) and (C) are mixed together in their total amount and emulsified, the emulsified particles may not be thinned or emulsified. In the case where emulsification is not performed or emulsified particles are not thinned, after a part of the components (a), (B), and (C) is added and emulsified, the remaining components (a) and (B) are added and emulsified, and after high-speed stirring is performed using HOMO MIXER or HOMO DISPER until the size of the emulsified particles becomes the target size, the remaining component (C) is added and diluted, whereby emulsification can be easily performed, and an oil-in-water type emulsified composition having fine emulsified particles and excellent storage stability can be obtained.

The emulsification temperature is not particularly limited, and is preferably not higher than the flash point of the oil-in-water emulsion composition of the present invention. Preferably 0 to 80 ℃ and more preferably 0 to 40 ℃. The emulsion is easily emulsified by setting the temperature to 0 to 80 ℃, and the emulsion composition becomes more stable. The stirring speed is preferably 100 to 10000rpm, more preferably 500 to 5000 rpm. The emulsification time is not particularly limited, and is preferably 1 to 240 minutes in the case of production using a batch emulsifier, and preferably 1 minute or less in the case of production using a continuous emulsifier. The pressure at the time of emulsification may be not only normal pressure but also reduced pressure or increased pressure. When stirring is performed under reduced pressure or increased pressure, air bubbles may not be easily mixed, and emulsification may be efficiently performed. The pressure at the time of pressure reduction is set to be higher than the vapor pressure of the raw material, thereby preventing volatilization of the raw material.

As the emulsifier, for example, HOMO MIXER (PRIMIX Corporation), HOMO DISPER (PRIMIX Corporation), AGI HOMO MIXER (PRIMIX Corporation), bi commix (PRIMIX Corporation) which is a 3-shaft type dispersion MIXER combining HOMO MIXER, HOMO DISPER and ANCHOR MIXER, colloid mill having a stirring part composed of a rotor and a stator (IKA Corporation, PUC Corporation, japan essence manufacturers, IWAKI & co., LTD.), high shear MIXER (silverson Corporation, PRIMIX Corporation), and HIVIS DISPER MIX 3D-5 (PRIMIXCorporation) which is a stirrer using revolution motion and rotation motion of 2 blades and high-speed rotation of a toothed blade, and the like can be used.

The viscosity of the oil-in-water emulsion composition is not particularly limited, but is preferably 5 to 20000 mPas, more preferably 10 to 5000 mPas, and further preferably 20 to 2000 mPas. If the absolute viscosity is less than 5 mPas, the storage stability may be lowered and repulsion may occur. On the other hand, if the absolute viscosity is larger than 20000 mPas, handling becomes difficult. The absolute viscosity of the oil-in-water type emulsion composition is a value at 25 ℃ measured by a BM type rotational viscometer.

The average particle diameter of the emulsified particles in the oil-in-water type emulsion composition is preferably 400nm or less, more preferably 350nm or less. If the average particle diameter is larger than 400nm, separation sometimes occurs immediately. The lower limit of the average particle size is not particularly limited, and may be usually 100nm or more, particularly 150mm or more. The average particle diameter can be measured by a dynamic light scattering method or a laser diffraction method. In the present invention, the volume average particle diameter (cumulative average diameter D) is obtained by a laser diffraction method₅₀(median diameter)). Examples of the device for the dynamic light scattering method include N4 PLUS (BECKMAN COULTER), Delsa Max CORE (BECKMAN COULTER), and Delsa Max Pro (BECKMAN COULTER), and examples of the device for the laser diffraction method include LA920 (manufactured by HORIBA) and LA960 (manufactured by HORIBA).

[ cosmetics ]

The oil-in-water emulsion composition of the present invention can be blended in skin cosmetics, hair cosmetics, and the like. In particular, from the characteristics of the present invention, it is preferable to blend the cosmetic composition in a makeup cosmetic composition or a skin care cosmetic composition. Examples of makeup cosmetics include foundations (including all solid and liquid), creams, makeup bases, lotions, eye shadows, lipsticks, blushes, eyebrow pencils, mascara, eyeliners, makeup remover, and skin creams. The form of the cosmetic is not particularly limited. For example, various forms such as liquid, emulsion, paste, solid, paste, gel, multilayer, mousse, spray, stick, pencil, and the like can be selected. The amount of the surfactant is preferably 1 to 70% by mass, more preferably 3 to 50% by mass, based on the cosmetic composition. In particular, the effects of the present invention can be easily obtained within this range, and if the amount of the additive is too large, the feeling of the composition may be heavy.

In the cosmetic of the present invention, various ingredients used in usual cosmetics can be blended within a range not impairing the effects of the present invention. Examples of the component include oils, compounds having alcoholic hydroxyl groups, surfactants, powders, compositions containing a cross-linked organopolysiloxane and an oil that is liquid at room temperature, silicone waxes, film-forming agents, antiperspirants, antibacterial agents, and other additives. These can be used alone in 1 or more than 2 kinds of appropriate combination.

Examples

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the examples. In the following examples, unless otherwise specified, "%" of the composition means mass%, and the ratio means a mass ratio. The kinematic viscosity is a measurement value at 25 ℃ measured with an austenite viscometer.

The following describes the components (A) and (B) used in examples and comparative examples.

< (A-1) Silicone resin

·(A-1[1])

From [ (CH)₃)₃SiO_0.5]_0.54[SiO₂]_0.46The silicone resin (molecular weight: 2000, viscosity at 36 ℃ C.: 20000 mPas, liquid state, content of SiOH group: 0.08mol/g)

[R₃SiO_0.5]Unit/[ SiO ]₂]Unit 1.2

·(A-1[2])

From [ (CH)₃)₃SiO_0.5]_0.57[SiO₂]_0.43The silicone resin (molecular weight: 1800, viscosity at 36 ℃ 10000 mPas, liquid state, content of SiOH group: 0.03mol/g)

[R₃SiO_0.5]Unit/[ SiO ]₂]Unit 1.3

·(A-1[3])

From [ (CH)₃)₃SiO_0.5]_0.41[SiO₂]_0.59The silicone resin shown (molecular weight 15000, solid at 36 ℃ content of SiOH groups: 0.05mol/g)

[R₃SiO_0.5]Unit/[ SiO ]₂]Unit is 0.7

The weight average molecular weight is a weight average molecular weight in terms of polystyrene obtained by GPC analysis.

The absolute viscosity is a value measured by a BM type rotational viscometer.

< (A-2) volatile oil

·(A-2[1]): decamethylcyclopentasiloxane (viscosity: 4 mm)²/s)

·(A-2[2]): isododecane (viscosity: 1.4 mm)²/s)

< (A) Silicone resin composition

·(A[1])

(A-1[1])/(A-2[1]) 90/10, viscosity: 1100mm²/s

·(A[2])

(A-1[1])/(A-2[2]) 90/10, viscosity: 1200mm²/s

·(A[3])

(A-1[2])/(A-2[2]) 90/10, viscosity: 400mm²/s

·(A[4])

(A-1[1])/(A-2[2]) 80/20, viscosity: 100mm²/s

Comparison product of (A5)

(A-1[1])/(A-2[2]) 60/40, ZhaoDegree: 20mm²/s

Comparison product of (A6)

(A-1[3])/(A-2[1]) 50/50, viscosity: 1900mm²/s

Comparison product of (A7)

(A-1[1])/(A-2[2]) 95/5, viscosity: 4500mm²/s

(B) polyoxyethylene sorbitan fatty acid ester

·(B[1])

Nonion OT-80 (polyoxyethylene sorbitan monooleate (20 E.O.); HLB 15.7)

·(B[2])

Nonion ST-60 (polyoxyethylene sorbitan monostearate (20 E.O.): HLB15.7, Nippon fat Co., Ltd.)

Surfactant [3] comparative product

NIKKOL Decaglyn 1-LV EX (lauric acid polyglycerol-10, HLB15.5, sunshine chemical Co., Ltd.)

Surfactant [4] comparative product

NIKKOL Decaglyn 1-SV EX (polyglycerin stearate-10, HLB12.5, Sun chemical Co., Ltd.)

(B1), (B2), (B3) and (B4) have the same structures as those recognized as food additives by the Ministry of health and labor.

[ example 1]

75g of silicone resin composition (A1), 3g of polyoxyethylene sorbitan fatty acid ester (B1) and 17g of water (C) were mixed, and stirred at 3000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation) to emulsify the mixture, and further 75g of silicone resin composition (A1) was added, and after stirred at 2000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation), 16.5g of polyoxyethylene sorbitan fatty acid ester (B1) was added, and stirred at 500rpm by T.K. HOMO DISPER (PRIMIX Corporation) for 3 minutes, and further stirred at 1500rpm for 20 minutes by T.K. HOMO DISPER (PRIMIX Corporation). Then, 113.5g of (C) water was added, and stirred at 1500rpm for 3 minutes using T.K. HOMO MIXER (PRIMIX corporation), to obtain an oil-in-water type emulsified composition (1). The emulsified particles of the emulsified composition (1) had an average particle diameter of 270nm and a viscosity of 110 mPas.

[ example 2]

75g of silicone resin composition (A2), 3g of polyoxyethylene sorbitan fatty acid ester (B1) and 17g of water (C) were mixed, and stirred at 3000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation) to emulsify the mixture, and further 75g of silicone resin composition (A2) was added, and after stirred at 2000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation), 16.5g of polyoxyethylene sorbitan fatty acid ester (B1) was added, and stirred at 500rpm by T.K. HOMO DISPER (PRIMIX Corporation) for 3 minutes, and further stirred at 1500rpm for 20 minutes by T.K. HOMO DISPER (PRIMIX Corporation). Then, 113.5g of (C) water was added, and stirred at 1500rpm for 3 minutes using T.K. HOMO MIXER (PRIMIX corporation), to obtain an oil-in-water type emulsified composition (2). The emulsified particles of the emulsified composition (2) had an average particle diameter of 260nm and a viscosity of 120 mPas.

[ example 3]

75g of the above silicone resin composition (A2), 3g of polyoxyethylene sorbitan fatty acid ester (B2) and 17g of water (C) were mixed, and stirred at 3000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation) to emulsify the mixture, and further 75g of the silicone resin composition (A2) was added, and after stirred at 2000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation), 16.5g of polyoxyethylene sorbitan fatty acid ester (B2) was added, and stirred at 500rpm by T.K. HOMO PER (PRIMIX Corporation) for 3 minutes, and further stirred at 1500rpm for 20 minutes by T.K. HOMO PER (PRIMIX Corporation). Then, 113.5g of (C) water was added, and stirred at 1500rpm for 3 minutes using T.K. HOMO MIXER (PRIMIX corporation), to obtain an oil-in-water type emulsified composition (3). The emulsified particles of the emulsified composition (3) had an average particle diameter of 260nm and a viscosity of 150 mPas.

[ example 4]

75g of silicone resin composition (A3), 3g of polyoxyethylene sorbitan fatty acid ester (B1) and 17g of water (C) were mixed, and stirred at 3000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation) to emulsify the mixture, and further 75g of silicone resin composition (A3) was added, and after stirred at 2000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation), 16.5g of polyoxyethylene sorbitan fatty acid ester (B1) was added, and stirred at 500rpm by T.K. HOMO DISPER (PRIMIX Corporation) for 3 minutes, and further stirred at 1500rpm for 20 minutes by T.K. HOMO DISPER (PRIMIX Corporation). Then, 113.5g of (C) water was added, and stirred at 1500rpm for 3 minutes using T.K. HOMO MIXER (PRIMIX corporation), to obtain an oil-in-water type emulsified composition (4). The emulsified particles of the emulsified composition (4) had an average particle diameter of 250nm and a viscosity of 180 mPas.

[ example 5]

75g of silicone resin composition (A2), 3g of polyoxyethylene sorbitan fatty acid ester (B1) and 19g of water (C) were mixed, and stirred at 3000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation) to emulsify the mixture, and 75g of silicone resin composition (A2) was added, and after stirring at 2000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation), 16.5g of polyoxyethylene sorbitan fatty acid ester (B1) was added, and stirred at 500rpm for 3 minutes by T.K. HOMO DISPER (PRIMIX Corporation), 3g of 1, 3-butanediol was added, and stirred at 500rpm for 3 minutes by T.K. HOMO DISPER (PRIMIX Corporation). Then, it was stirred at 1500rpm for 20 minutes using T.K. HOMO ISPER (PRIMIX Corporation), and then, 108.5g of (C) water was added, and it was stirred at 1500rpm for 3 minutes using T.K. HOMO MIXER (PRIMIX Corporation), to obtain an oil-in-water type emulsified composition (5). The emulsified particles of the emulsified composition (5) had an average particle diameter of 250nm and a viscosity of 200 mPas.

[ example 6]

75g of silicone resin composition (A2), 3g of polyoxyethylene sorbitan fatty acid ester (B1) and 17g of water (C) were mixed, stirred at 3000rpm for 3 minutes using T.K. HOMO MIXER (PRIMIX corporation), emulsified, further, 75g of silicone resin composition (A2) was added thereto, and after stirring at 2000rpm for 3 minutes using T.K. HOMO MIXER (PRIMIX corporation), adding 16.5g of polyoxyethylene sorbitan fatty acid ester (B1), stirring at 500rpm for 3 minutes using T.K. HOMODISPER (PRIMIX Corporation), further, the mixture was stirred at 1500rpm for 20 minutes by T.K. HOMO DISPER (PRIMIXCORPORATION), then, 83.5g of (C) water was added, and stirred at 1500rpm for 3 minutes using T.K. HOMO MIXER (PRIMIX corporation), further, (E) 30g of polyvinyl alcohol (10% Gohsenol EG-40C (Nippon synthetic chemical Co., Ltd)) was added thereto, and the mixture was stirred at 1500rpm for 3 minutes to obtain an oil-in-water emulsion composition (6). The emulsified particles of the emulsified composition (6) had an average particle diameter of 260nm and a viscosity of 1000 mPas.

[ example 7]

75g of silicone resin composition (A2), 3g of polyoxyethylene sorbitan fatty acid ester (B1) and 17g of water (C) were mixed, and stirred at 3000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation) to emulsify the mixture, and further 75g of silicone resin composition (A2) was added, and after stirred at 2000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation), 16.5g of polyoxyethylene sorbitan fatty acid ester (B1) was added, and stirred at 500rpm by T.K. HOMO DISPER (PRIMIX Corporation) for 3 minutes, and further stirred at 1500rpm for 20 minutes by T.K. HOMO DISPER (PRIMIX Corporation). Then, 98.5g of (C) water was added, and stirred at 1500rpm for 3 minutes using T.K. HOMO MIXER (PRIMIX corporation). Further, (F) 15g of colloidal silica (40% aqueous dispersion of colloidal silica (COSMO S-40, Nissan catalytic chemical Co., Ltd)) was added thereto, and the mixture was stirred at 1500rpm for 3 minutes to obtain an oil-in-water emulsion composition (7). The emulsified particles of the emulsified composition (7) had an average particle diameter of 260nm and a viscosity of 80 mPas.

[ example 8]

75g of silicone resin composition (A4), 3g of polyoxyethylene sorbitan fatty acid ester (B2) and 23g of water (C) were mixed, and stirred at 3000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX corporation) to emulsify the mixture, and 75g of silicone resin composition (A4) was added, and stirred at 2000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX corporation), and further stirred at 500rpm by T.K. HOMO DISPER (PRIMIX corporation) to stir 16.5g of polyoxyethylene sorbitan fatty acid ester (B2) and then stirred at 1500rpm for 50 minutes by T.K. HOMO PER (PRIMIX corporation). Then, 107.5g of (C) water was added, and stirred at 1500rpm for 3 minutes using T.K. HOMO MIXER (PRIMIX corporation), to obtain an oil-in-water type emulsified composition (8). The emulsified particles of the emulsified composition (8) had an average particle diameter of 260nm and a viscosity of 200 mPas.

Comparative example 1

75g of silicone resin composition (A5), 3g of polyoxyethylene sorbitan fatty acid ester (B1) and 23g of water (C) were mixed, and stirred at 500rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX corporation) to emulsify the mixture, and 75g of silicone resin composition (A4) was added, and after stirred at 2000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX corporation), 16.5g of polyoxyethylene sorbitan fatty acid ester (B1) was added, and stirred at 500rpm for 3 minutes by T.K. HOMO PER (PRIMIX corporation) to stir at 1500rpm for 20 minutes by T.K. HOMO PER (PRIMIX corporation). Then, 107.5g of (C) water was added, and stirred at 1500rpm for 3 minutes using T.K. HOMO MIXER (PRIMIX corporation), to obtain an oil-in-water type emulsified composition (9). The emulsified particles of the emulsified composition (9) had an average particle diameter of 400nm and a viscosity of 300 mPas.

Comparative example 2

75g of silicone resin composition (A6), 3g of polyoxyethylene sorbitan fatty acid ester (B1) and 17g of ion-exchanged water (C) were mixed, and stirred at 1000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation) to emulsify the mixture, and further 75g of silicone resin composition (A5) was added, and after stirred at 2000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation), 16.5g of polyoxyethylene sorbitan fatty acid ester (B1) was added, and stirred at 500rpm by T.K. HOMO DISPER (PRIMIX Corporation) for 3 minutes, and further stirred at 1500rpm for 20 minutes by T.K. HOMO DISC (PRIMIX Corporation). Then, 113.5g of (C) water was added, and stirred at 1500rpm for 3 minutes using T.K. HOMO MIXER (PRIMIX corporation), to obtain an oil-in-water type emulsified composition (10). The emulsified particles of the emulsified composition (10) had an average particle diameter of 300nm and a viscosity of 80 mPas.

Comparative example 3

75g of silicone resin composition (A7), 3g of polyoxyethylene sorbitan fatty acid ester (B1) and 17g of water (C) were mixed, and stirred at 3000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation) to emulsify the mixture, and further 75g of silicone resin composition (A6) was added, and after stirred at 2000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation), 16.5g of polyoxyethylene sorbitan fatty acid ester (B1) was added, and stirred at 500rpm by T.K. HOMO DISPER (PRIMIX Corporation) for 3 minutes, and further stirred at 1500rpm for 20 minutes by T.K. HOMO DISPER (PRIMIX Corporation). Then, 113.5g of (C) water was added, and stirred at 1500rpm for 5 minutes using T.K. HOMO MIXER (PRIMIX corporation), to obtain an oil-in-water type emulsified composition (11). The emulsified particles of the emulsified composition (11) had an average particle diameter of 270nm and a viscosity of 150 mPas.

Comparative example 4

75g of silicone resin composition (A2), 1.8g of surfactant [3], 1.2g of surfactant [4], and 17g of water (C) were mixed, and stirred at 3000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation) to emulsify, and 75g of silicone resin composition (A2) was added, and after stirred at 2000rpm for 3 minutes by T.K. HOMO MIXER (PRIMIX Corporation), 9.9g of surfactant [3], 6.6g of surfactant [4] were added, and stirred at 500rpm for 3 minutes by T.K. HOMO DISPER (PRIMIX Corporation) to stir at 1500rpm for 20 minutes. Then, 113.5g of (C) water was added, and stirred at 1500rpm for 3 minutes using T.K. HOMO MIXER (PRIMIX corporation), to obtain an oil-in-water type emulsified composition (12). The emulsified particles of the emulsified composition (12) had an average particle diameter of 350nm and a viscosity of 50 mPas.

The evaluation results of the oil-in-water emulsion compositions (1 to 12) obtained in the above examples on the compounding composition (%), average particle diameter, viscosity, centrifugal separation stability, coatability and cracking property are shown in the following table. The average particle diameter was measured by HORIBA LA920(HORIBA, Ltd.), and the viscosity of the composition was measured at 25 ℃ by using a BM type rotational viscometer.

[ stability in centrifugal separation ]

About 25g of the emulsified composition (1 to 12) was put into a centrifugal separation tube, and after centrifugation was carried out for 50 minutes at 3000rpm by a centrifugal separator H-19FM (コクサン Co., Ltd.), nonvolatile components in the upper and lower parts were measured (105 ℃ C., 3 hours). The result is represented by the nonvolatile content in the upper layer divided by the nonvolatile content in the lower layer. The nonvolatile component of the upper layer part is divided by the nonvolatile component of the lower layer part, and the obtained value is 0.95-1.05. The more the value is a value deviated from 1, the more likely the value is separated with time.

[ coatability ]

The emulsion composition (1 to 12) was applied to a thick paper (15 cm. times.7 cm) whose surface had not been coated with a No.13 bar coater (film thickness: about 20 μm), and then dried at 36 ℃ for 30 hours to evaluate repellency.

< coating Property determination Standard >

○ No repulsion-less than 30% of the total coated surface has repulsion

△ the coated surface has repellency of more than 30% and less than 50% of the whole

X: more than 50% of the whole coated surface has repellency

"△" or "○" was set as pass.

[ crack Property ]

The thick paper evaluated for coatability was wound into a cylinder having a diameter of 3.5cm, and cracks were evaluated.

< criterion for determining cracking >

○ no cracking

X: has cracks

[ Table 1]

[ Table 2]

EXAMPLE 9 Mascara

< preparation method >

Bentonite (2) was added to a part of water (1), and after sufficiently swelling with HOMO MIXER, the mixture was added to water (3) to (9), and stirred.

The mascara using the emulsion composition (2) or the emulsion composition (9) has a uniform coating film and good persistence, and particularly the mascara when the emulsion composition (2) is blended has good persistence.

[ example 9] O/W cream

(Note 1) the trade name of shin-Etsu chemical industry, Ltd.: metholose SM-4000

(Note 2) manufactured by SEPPIC: sepigel 305

< preparation method >

A: the components (3) to (9) were mixed.

B: mixing the components (1) and (2), adding the component A, stirring and emulsifying.

These creams using the emulsion compositions (2) and (9) were not sticky, spread well during application, and felt a close feeling to the skin, particularly when the emulsion composition (2) was used.

Claims

(A-1) has [ R ]₃SiO_0.5]Unit and [ SiO₂]Unit, with [ R₃SiO_0.5]Unit/[ SiO ]₂]A silicone resin having a molar ratio of units of 0.7 to 1.4, wherein R is the same or different 1-valent organic group having 1 to 10 carbon atoms,

(A-2) a volatile oil,

(C) water: 20 to 62 mass%.

2. The oil-in-water emulsion composition according to claim 1, wherein the average particle diameter of the emulsified particles is 400nm or less.

3. The oil-in-water type emulsified composition according to claim 1 or 2, wherein the component (A-2) is selected from hydrocarbon oils and has a viscosity of 2mm at 25 ℃²1 or more volatile oils in silicone oil with a concentration of less than or equal to s.

4. The oil-in-water emulsion composition according to any one of claims 1 to 3, wherein the component (B) is 1 or more selected from the group consisting of polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate and polyoxyethylene sorbitan monopalmitate.

5. The oil-in-water emulsion composition according to any one of claims 1 to 4, wherein the component (A-1) is represented by [ R₃SiO_0.5]Unit/[ SiO ]₂]The molar ratio of the units is 1.1 to 1.4.

6. The oil-in-water emulsion composition according to any one of claims 1 to 5, wherein the component (A-1) is a liquid silicone resin having a viscosity of 5000 mPas or higher at 36 ℃.

7. The oil-in-water emulsion composition according to any one of claims 1 to 6, further comprising 0.1 to 5% by mass of (D) an ingredient selected from the group consisting of 1, 3-butanediol, glycerin, maltitol, sorbitol, 1, 2-pentanediol, 1, 2-hexanediol, polyethylene glycol and trimethylglycine.

8. The oil-in-water emulsion composition according to any one of claims 1 to 7, further comprising 0.1 to 5% by mass of (E) a water-soluble polymer compound.

9. The oil-in-water emulsion composition according to any one of claims 1 to 8, further comprising 0.1 to 10 mass% of (F) synthetic amorphous silica.

10. A cosmetic material comprising the oil-in-water emulsion composition according to any one of claims 1 to 9.